Facile synthesis of one-dimensional peapod-like Sb@C
submicron-structures
Luo, W., Lorger, S., Wang, B., Bommier, C., & Ji, X. (2014). Facile synthesis of
one-dimensional peapod-like Sb@C submicron-structures. Chemical
Communications, 50(41), 5435-5437. doi:10.1039/c4cc01326c
10.1039/c4cc01326c
Royal Society of Chemistry
Accepted Manuscript
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Facile synthesis of one-dimensional peapod-like Sb@C submicronstructures
Wei Luo, Simon Lorger, Bao Wang, Clement Bommier and Xiulei Ji*
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Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
We demonstrate a novel synthetic route to fabricate a onedimensional peapod-like Sb@C structure with disperse Sb
submicron-particles encapsulated in carbon submicron-tubes.
The synthetic route may well serve as a general methodology
for fabricating carbon/metallic fine structures by thermally
reducing their carbon-coated metal oxide composites.
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Submicron- and nano-structured materials have attracted great
interest due to their superior physicochemical properties and wide
applications.1 Particularly, one-dimensional (1D) structures such
as wires, tubes and fibers have attracted much attention.2 Intense
efforts have been made to design and prepare various 1D
structures with innovative synthetic schemes.3 To date, most
synthetic methodologies are based on template-assisted methods,4
self-assembly5 or chemical vapor deposition,6 which can be timeconsuming or costly. Therefore, developing simple but efficient
synthetic strategies to fabricate 1D structures still remains a great
challenge.
Antimony (Sb) and its compounds have been extensively
investigated due to their wide applications in lead-acid batteries,
fire retardants, micronelectronics and medicines.7 Recently, there
has been increasing interest in employing Sb and its compounds
as anodes for rechargeable lithium-ion or sodium-ion batteries.8
Owing to the alloying/dealloying reaction mechanism, these
materials have higher theoretical capacities compared to the
intercalation compounds (e.g., graphite and Li4Ti5O12). However,
like other alloying-type anodes (e.g., Si and Sn), these Sb-based
anodes encounter a large volumetric change upon electrochemical
cycling, which results in fast capacity fading. In order to
overcome this issue, ongoing research efforts have focused on
controlling the morphology into submicron- or nano-sizes8e,9 or
coating with a carbon layer.10 Very recently, 1D Sb/C fibers have
been fabricated by electrospinning a SbCl3/polyaniline (PAN)
solution.11 These 1D Sb/C fibers have shown a high capacity and
enhanced cycle life.
In this communication, we present a novel synthetic route for
the fabrication of 1D peapod-like Sb@C with disperse Sb
submicron-particles encapsulated in carbon submicron-tubes by
using bulk Sb powder as a precursor. As illustrated in Scheme 1,
Sb2O3 submicron-wires (Sb2O3 SWs) are first prepared by direct
air-oxidation of bulk Sb powder (~ 100 mesh) soaked in a
mixture solution of a poly(vinyl pyrrolidone) (PVP) /
ethylenediamine (EDA)/H2O, as reported previously.12 Later, the
as-prepared Sb2O3 SWs are coated with a layer of glucoseThis journal is © The Royal Society of Chemistry [year]
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derived carbon via a hydrothermal reaction, which gives an
intermediate product (referred to as Sb2O3@C). Then, a thermal
reduction at 500 ºC for 2 hrs under N2/H2 (5% in volume)
converts Sb2O3@C to 1D peapod-like structure with disperse Sb
submicron-particles trapped in the “carbon submicron-tube pods”.
Moreover, much void space appears in the carbon tubes due to
the contraction from Sb2O3 SWs to Sb submicron-particles. We
refer to the 1D peapod-like structure as Sb@C.
The crystalline structures of various materials are revealed by
X-ray diffraction (XRD). As shown in Fig. 1a, bulk Sb powder
exhibits a typical hexagonal phase of metallic Sb (JCPDS No. 350732). After the oxidation, the as-formed phase can be readily
indexed to orthorhombic Sb2O3 (JCPDS No. 11-0689) (Fig. 1b).
Moreover, the intensities of the (110) and (200) peaks in Sb2O3
SWs are greatly enhanced in comparison to the bulk counterpart,
indicative of a strong orientation preference of wires along the
[001] direction.12 After the hydrothermal carbon coating, the
crystalline structure of Sb2O3@C remains the same (Fig. 1c). The
final product of Sb@C exhibits the crystalline phase of hexagonal
Sb, indicating the successful thermal reduction (Fig. 1d). Raman
spectroscopy was further carried out (Fig. S1, see ESI†). Sb2O3
SWs exhibit typical Sb2O3 Raman shifts, displaying peaks at
∼196, 225, 293, 380, 408, 455, and 503 cm−1.12a Sb@C displays
similar Raman peaks as those from bulk Sb powder,
corroborating the XRD results (Fig. 1). Moreover, Raman shifts
from carbon (∼1350 and 1590 cm−1) suggest the existence of
carbon in Sb@C. Furthermore, the ID/IG ratio of 0.91 suggests
that the carbon layer is amorphous, which should be ascribed to
the relatively-low thermal treatment temperature. The carbon
content in the Sb@C is determined as ~ 25 wt% by
thermogravimetric analysis (TGA), assuming the complete
carbon combustion and formation of Sb2O4 at 800 °C (Fig. S2,
see ESI†).11b
Scheme 1 Schematic illustration for the formation of 1D peapod-like
Sb@C submicro-structure by a simple oxidation-carbon coatingreduction route.
[journal], [year], [vol], 00–00 | 1
Fig. 2 Low and high-magnification FESEM images of bulk Sb
powder (a, b), Sb2O3 NWs (c, d), and Sb@C (e, f).
Fig. 1 XRD patterns of (a) bulk Sb powder, (b) Sb2O3 SWs, (c)
Sb2O3@C and (d) Sb@C.
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Field-emission scanning electron microscopy (FESEM) images
provide the morphological information of the materials. As
shown in Fig. 2a and b, bulk Sb powder is well crystallized with
particle sizes ranging from 5 to 40 μm. After oxidation, the asformed Sb2O3 is composed of 1D submicron-wires with an
average diameter of 800 nm and lengths up to tens of microns
(Fig. 2c). When zoomed in, a smooth surface of Sb2O3 SWs is
evident (Fig. 2d). The energy-dispersive X-ray (EDX) analysis
confirms that the atomic ratio between Sb and O is ~2/3 in Sb2O3
SWs (Fig. S3, see ESI†). The growth mechanism of Sb2O3 SWs
has been discussed by Deng et al. Sb is oxidized by dissolved
oxygen in H2O where EDA and PVP act as a catalyst and surface
stabilizer, respectively.12 After the hydrothermal carbon coating,
the submicron-wire morphology is well maintained (Fig. S4, see
ESI†). Compared to the EDX spectrum of Sb2O3 SWs, a new
sharp peak of carbon appears after carbon coating (Fig. S3, see
ESI†). After thermal treatment, the 1D shape is well maintained
as well, and slight shrinkage in diameter is observed (Fig. 2e and
f). Interestingly, the Sb2O3 wires encapsulated in carbon shells
are converted to disperse Sb submicron-particles in the carbon
submicron-tubes, exhibiting a peapod-like structure. Surprisingly,
phase agglomeration does not occur when Sb2O3 is converted to
Sb under thermal reduction. It is worth noting that the carbon
coating plays a critical role for maintaining the 1D morphology of
the composite. More FESEM images are provided in the
supporting information to show the unique 1D peapod-like
structure of Sb@C (Fig. S5, see ESI†).
Fig. 3a shows a typical transmission electron microscope
(TEM) image of an individual Sb2O3 submicron-wire. The
corresponding high-resolution TEM (HRTEM) image taken on
the edge is shown in Fig. 3b. The well-resolved lattice fringe with
an inter-plane distance of ~1.25 nm is indexed to the (010) plane
of the orthorhombic Sb2O3.12 The selected-area electron
diffraction (SAED) pattern reveals the single-crystal nature of the
Sb2O3 SWs along the [001] direction (Fig. 3c), which is
consistent with the XRD results and previous reports.12 The 1D
peapod-like morphology of Sb@C is further confirmed by TEM
studies (Fig. S6, see ESI†). Zoomed-in TEM observation shows
two disperse Sb submicron-particles are encapsulated in the
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Fig. 3 TEM, HRTEM images and SAED patterns of Sb2O3 SWs (a,
b, c) and Sb@C (d, e, f). (g) HAADF-STEM and (h, i)
corresponding elemental mapping images of Sb@C.
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carbon submicron-tubes (in Fig. 3d). The HRTEM image taken
on the red area marked in Fig. 3d further reveals the amorphous
carbon structure for the carbon submicron-wires (Fig. 3e), which
is typical for the sugar-derived carbon.13 Moreover, the lattice
fringe with an inter-plane spacing of 0.33 nm from the Sb
nanoparticle should be attributed to the (012) planes. The
corresponding SAED pattern also suggests the single-crystal
nature of Sb (Fig. 3f). Furthermore, Fig. 3g-i show the high angle
annular dark field-scanning TEM (HAADF-STEM) and the
corresponding EDX mapping images of Sb@C, confirming the
peapod-like structure with a clear contrast.
Sodium-ion storage property of the as-prepared Sb@C was
studied by galvanostatic discharge-charge measurements using
Na metal as the counter electrode and an electrolyte of 1.0 mol/L
NaPF6 in ethylene carbonate / diethyl carbonate (EC/DEC).
Voltage plateaus are exhibited at about 0.5 V and 0.8 V in the
discharge and charge curve, respectively (Fig. S7, see ESI†),
suggesting a typical two-phase alloying reaction.9 The first
discharge and charge capacity are ~335 and 230 mAh/g,
respectively, based on the total mass of Sb@C composites. The
irreversible capacity in the first cycle may be attributed to the
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formation of solid electrolyte interphase (SEI) on carbon. We
recognize that the charge capacity of this composite is low. This
can be due to the following issues. Firstly, the particle size of Sb
phase is still relatively large, which may limit the utilization of Sb.
Secondly, the electronic conductivity of the glucose-derived
carbon as a coating layer is low due to the low carbonization
temperature used.8d,8e,11 Further optimization is undergoing in our
lab.
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Conclusions
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In summary, we have demonstrated a facile strategy for the
fabrication of 1D peapod-like Sb@C submicron-structures with
Sb submicron-particles and large void space encapsulated in the
carbon submicron-tubes. Considering the low cost of the starting
materials and simple synthetic process, we believe our method
may shed some light on a scalable fabrication of Sb-based
materials and other peapod-like structures.
Acknowledgements
The authors acknowledge the financial support from Advanced
Research Projects Agency-Energy (ARPA-E), Department of
Energy of the United States, Award number: DEAR0000297TDD. We are thankful to Ms. Teresa Sawyer and Dr.
Peter Eschbach for the SEM and TEM measurements in OSU EM
Facility, funded by National Science Foundation via the Major
Research Instrumentation Program under Grant No. 1040588,
Murdock Charitable Trust and the Oregon Nanoscience and
Microntechnologies Institute. We appreciate the help from
Professor Chih-Hung Chang and Mr. Changqing Pan for Raman
analysis.
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Notes and references
Department of Chemistry, Oregon State University, Corvallis, OR 973314003, USA. Tel: 001 541-737-6798; E-mail: david.ji@oregonstate.edu
† Electronic Supplementary Information (ESI) available: Experimental
details and additional data. See DOI: 10.1039/b000000x/
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